Olefin hydroformylation

ABSTRACT

Organic compound conversion in the presence of a new class of heterogeneous catalyst is provided. Said new class of heterogeneous catalyst comprises a substrate having a minimum surface area of about 10 m2/g and having pores with a minimum pore diameter of about 5 Angstrom Units, said substrate being modified by at least one amine functional member coordinated to a metal function, said amine functional member acting as a bridging member between said substrate and said metal function.

CROSS-REFERENCE TO RELATED APPLICATION

This is a continuation of application Ser. No. 753,749, filed Dec. 23,1976, now abandoned, which is a division of application Ser. No.681,883, filed Apr. 30, 1976, now abandoned, which is acontinuation-in-part of application Ser. No. 443,557, filed Feb. 19,1974, now U.S. Pat. No. 3,980,583.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to organic compound conversion with a new classof heterogeneous catalyst having exceptional chemical and thermalstability, high upper reaction temperature limits and good catalyticactivity for conversion of organic compounds, said catalyst comprising asubstrate which is modified by at least one amine functional membercoordinated to a metal function, said amine functional member acting asa bridging member between said substrate and said metal function.

2. Description of Prior Art

There has long been a need for effective, commercially practicabletransition metal catalysts for such reactions as hydrogenation,hydroformylation, carbonylation, dimerization and others. Earlycatalysts developed for such purposes were homogeneous catalysts whichsuffered from, among other things, the expense of recovering,repurifying and recycling said catalysts. Changes in selectivity andreactivity were often brought about by varying ligands and by changes inoperating conditions, such as, for example, temperature, pressure,reactant ratios, reaction rates and others. Catalyst losses were oftenso high that relatively inexpensive metals such as cobalt were used,even though such catalysts required severe operating conditions.Catalysts which were effective under somewhat milder conditions, such asrhodium complexes, were much more expensive (of the order of 10³ timesas expensive), and, therefore, to insure low catalyst loss, created therequirement of costly recovery systems.

More recently, a number of heterogeneous catalysts have been developed(Belgium patent No. 721686) which demonstrate activities andselectivities for certain reactions, such as, for example,hydroformylation. Those heterogeneous catalysts are comprised oftransition metal complexes on ligands bonded to macroporous resins andshow superior catalytic results in certain reactions, such ashydroformylation, when compared to their homogeneous analogues. However,the utility of said heterogeneous catalysts is limited by the relativelylow chemical and thermal stability of the resin supports therein.

Another class of heterogeneous catalyst has been developed comprisingcomplexed transition metals on phosphine ligands bonded to inorganicoxide surfaces (Dutch Patent No. 7,018,453 and British Pat. No.1,275,733). This class of catalysts has been shown to be useful in thehydroformylation reaction (Dutch Patent No. 7,018,322).

The instant invention of organic compound conversion with a new class ofheterogeneous catalyst, which catalyst comprises a substrate having aminimum surface area of about 10 m² /g and having pores with a minimumpore diameter of about 5 Angstrom Units, said substrate being modifiedby at least one amine functional member coordinated to a metal function,said amine functional member acting as a bridging member between saidsubstrate and said metal function, is demonstrated to provide benefitsunmatched by use of prior resin-bound heterogeneous catalysts oroxide-bound phosphine functionalized heterogeneous catalysts. Thecatalyst for use in this invention has enhanced organic compoundconversion activity, e.g. olefin isomerization activity, relative toother oxide-bound or resin-bound complexes. With respect to catalyticactivity, the catalyst for use herein shows dual-functional catalyticactivity, e.g. in which an olefin is hydroformylated to an aldehydewhich is then converted by an acid functionality of the catalyst to anacetal in the presence of an alcohol.

SUMMARY OF THE INVENTION

In accordance with the present invention there is provided a novelmethod of organic compound conversion which comprises contacting saidorganic compound under organic compound conversion conditions with acatalytically effective amount of a catalyst comprising a substrateconsisting of a porous solid refractory inorganic oxide, e.g. zeolite,having a minimum surface area of about 10 m² /g, preferably a minimum ofabout 200 m² /g, and having pores with a minimum pore diameter of about5 Angstrom Units, preferably a minimum of about 100 Angstrom Units, saidsubstrate being modified by at least one amine functional membercoordinated to a metal function, said amine functional member acting asa bridging member between said substrate and said metal function.

DESCRIPTION OF PREFERRED EMBODIMENTS

The catalyst for use in the instant invention is a new class ofheterogeneous catalyst displaying exceptionally valuable properties inorganic compound conversion processes. The catalyst comprises asubstrate having certain specific and essential modifications. Thesubstrate may be one of a number of solid porous inorganic oxides, e.g.zeolites, having surface hydroxyl groups, provided that said inorganicoxide has a minimum surface area of about 10 m² /g and pores with aminimum pore diameter of about 5 Angstrom Units. Non-limiting examplesof said substrate include those having a major component of silica oralumina or both, such as, for example, alumina, siliceous materials,open lattice clays and crystalline aluminosilicates.

Non-limiting examples of siliceous materials useful as said substrateinclude silica and combinations thereof with oxides of metals of GroupsII-A, III-A, III-B, IV-A, IV-B and V-B of the Periodic Table ofElements, such as, for example, silica-alumina, silica-magnesia,silica-zirconia, silica-thoria, silica-berylia, silica-titania, as wellas ternary compositions of silica, such as, for example,silica-alumina-thoria and silica-alumina-zirconia.

Non-limiting examples of crystalline aluminosilicate materials useful asthe substrate of the catalyst include the synthetic zeolites X, Y,ZSM-4, ZSM-5, ZSM-11, ZSM-35, ZSM-38 and others, and naturally occurringzeolites, such as erionite, faujasite, mordenite and others.

Non-limiting examples of open lattice clays useful as the substrate ofthe catalyst include bentonite and montmorillonite and others.

The solid porous refractory oxide for use herein as said substrate mayhave deposited or exchanged thereon one or more of various metalcomponents in keeping with the spirit and scope of the invention. Forexample, alumina and a siliceous material as above defined may havedeposited thereon a metal of Groups VI-B or VIII of the Periodic Tableof the Elements, e.g. Co and Mo, or an oxide of such a metal, e.g. MoO₃and CrO₃. Also, for example, a crystalline aluminosilicate for useherein may have exchanged thereon hydrogen or metal cations of GroupsIA-VIII of the Periodic Table, especially metals of Groups II and III,including the rare earth metals, tin, lead, metals of the actinideseries, antimony, bismuth and chromium or combinations thereof. Further,a crystalline aluminosilicate for use herein may be incorporated into anaturally-occurring inorganic material, such as, for example clay andmetal oxides.

Specific modifications to the substrate chosen for the catalyst includeat least one amine functional member, containing the element silicon,coordinated to a metal function, said amine functional member acting asa bridging member between said substrate and said metal function. Saidamine function exists, when in a bridging position between saidsubstrate and said metal function, as a ligand covalently bonded to saidsubstrate. The functionalization, i.e. covalently bonding said amineligand to said substrate, of said substrate can be either exterior orinterior of said substrate.

The metal function complexed to said amine ligand bridging member may beany one or more of a series of metals recognized in the art astransition metals selected from the group consisting of Group VIIImetals of the Periodic Table of Elements. Non-limiting examples of suchmetals include iron, cobalt, nickel, ruthenium, rhodium, palladium,iridum, platinum and osmium.

Said metal functions for complexing to said amine ligand functions maybe in the form of, by way of non-limiting examples, halides, e.g.fluorides, chlorides and iodides; oxides; sulfides; sulfates,carbonates, carboxylates and nitrates.

Non-limiting examples of said catalyst, therefore, include thefollowing, wherein X is said complexed metal functions: ##STR1##

In synthesis of the catalyst for use in the present invention thegeneral method may be employed in which a suitable substrate, i.e. aporous solid inorganic refractory oxide, having surface hydroxyl groups,e.g., silica, silica-alumina, alumina, a natural zeolite such as, forexample, erionite, and a synthetic zeolite such as, for example, ZSM-5,is allowed to react with a suitable alkyl substituted compound ofsilicon, in acid or base catalysis, if desired. The above alkylcompounds must contain a functional group on the silicon atom, as forexample, hydro, amino, amido, carboxy, alkoxy or halogen which willcondense with hydroxyl groups to give a covalent bond. Said alkylcompound must also have on the alkyl moiety one or more ligands (orgroups which may be converted to ligands via conventional organicchemistry) suitable for bonding transition metal complexes which havedesirable catalytic properties, i.e. metals from Group VIII.

More specifically, the method of preparing a catalyst for use herein mayinclude suspending said porous solid inorganic oxide substrate in asolution of an appropriate amino alkyl substituted compound of silicon,for example a silane, in xylene or another suitable solvent, refluxingthe resulting mixture for a suitable time, such as, for example, 2-6hours, cooling the mixture and washing it with a suitable solvent, suchas, for example, hexane, in which said silane is soluble, and thendrying the resultant product in a vacuum, such as, for example, in avacuum oven, at an elevated temperature of, for example, 100° C. toabout 150° C. The individual steps of this method may be separated bylong periods of time without detrimental results.

For preparation of the insoluble oxide-bound metal compound complex, asolution of soluble coordination compound having at least two ligandsconnected to at least one central metal atom is mixed with the insolublefunctionalized oxide. Upon mixing of the coordination compound with thefunctionalized oxide, the two react with the functional group of theoxide replacing one or more of the ligands of the coordination compound,thereby chemically bonding the coordination compound to the oxidethrough at least one bond which joins the central metal atom to afunctional group.

The ligands of the soluble coordination compound may be ionic, neutralor mixed ligands. Anionic ligands include chloride, bromide, iodide,cyanide, nitrate, sulfate, acetate, sulfide, and trichlorostanniteligands. Neutral ligands include water, ammonia, phosphine, carbonmonoxide, olefin, and diolefin ligands.

The central metal atom of the soluble coordination compound may be anyGroup VIII metal. Preferably, the central metal atom is selected fromthe group consisting of platinum, palladium, rhodium, ruthenium, osmiumand iridium. Usually, the soluble coordination compound will have onecentral metal atom. However, it may have two central metal atoms, eitherthe same or different.

Examples of suitable coordination compounds are potassiumtetrachloropalladite, chloroplatinic acid, rhodium trichloridetrihydrate, dichlorobis (triphenylphosphine) palladium (II),dichlorotetrakis-(triphenylphosphine) ruthenium (II),chlorobis(triphenylphosphine) rhodium (I), tricarbonylbis(triphenylphosphine) ruthenium (O), iodocarbonylbis (triphenylphosphine)iridium (I), potassium tetranitroplatinate (II), tetra (pyridine)platinum (II) tetrabromoplatinate, tetraaminepalladium (II) chloride,di-mu-chlorodichlorobis (triethylarsine) diplatinum (II),di-mu-thiocyanatodithiocyanatobis (tripropylphosphine) diplatinum (II)and potassium trichloro (trichlorostannato) platinite (II).

Solvents for the soluble coordination compounds include water, methanol,ethanol, butanol, acetic acid, chlorinated hydrocarbons such aschloroform, various ethers such as diethyl ether, acetone, and dimethylsulfoxide.

The solution of the soluble coordination compound and the functionalizedoxide, upon mixing, is subjected to agitation at a temperature and for atime to effect bonding of a desired amount of the coordination compoundto the functionalized oxide. Agitation may be effected simply bystirring. However, other conventional means of agitation may beemployed. The temperature may range from between room temperature tojust below the decomposition temperature of either the coordinationcompound or the amine functional bridging member. Preferably,temperatures between room temperature and the boiling point of thesolvent for the coordination compound are employed. The rate at whichthe coordination compound reacts with the functionalized oxide depends,of course, on the temperature, the rate increasing with temperature. Thetime of agitation may range from a fraction of an hour, say one-quarterof an hour, to several hours, say twelve hours, or even one or moredays, say three days.

Following reaction of the coordination compound and the functionalizedoxide, the resulting insoluble oxide-bound metal compound complex isseparated from the product mixture. Separation may be by anyconventional means. Thus separation may be by settling of the complexand decantation of the liquid portion of the product mixture. Separationmay also be made by filtration or centrifugation. The complex then maybe washed to remove adhering and absorbed solvent and any unreacteddissolved coordination compound. Washing, for example, may be withwater, followed by ethanol, and then with ether. Thereafter, the complexmay be dried.

The insoluble oxide-bound metal compound complex will be insoluble inthe materials, heretofore mentioned, in which the original oxide portionof the complex is insoluble. Thus, the complex will be insoluble inwater, hydrocarbons such as benzene, alcohols, aldehydes, ethers,ketones, organic acids, carbon disulfide, thiols, amines, and others.Further, the metal of the coordination compound being bonded chemicallyto the functionalized oxide will also be insoluble in these samematerials.

The final catalyst for use herein may comprise 0.01 to 30 percent,preferably 0.1 to 10 percent, by weight of metal; 0.1 to 25 percent, andpreferably 2 to 10 percent, by weight of amine-functional ligand; andabout 60 to 99.9 percent by weight of oxide. The sum of the amount ofthe ligand and metal preferably should not exceed 25 percent.

The production of an insoluble oxide-bound metal compound complex may beillustrated employing, as a soluble coordination compound having anionicligands, potassium tetrachloropalladite, K₂ PdCl₄, and an insolublefunctionalized silica. The coordination compound is dissolved in waterand then mixed with the functionalized oxide. The coordination compoundreacts with the functionalized oxide according to the followingequation: ##STR2##

The insoluble oxide-bound metal compound complexes may be seen tocomprise an insoluble functionalized oxide containing basic functionalgroups and chemically bonded to some of the functional groups are metalatoms, the metals having been set forth hereinabove. The bonding occursas a result of coordination of the functional group of the oxide to themetal. The metal atoms preferably have chemically bonded thereto atleast one ligand, the ligands also having been set forth hereinabove.For example, the insoluble metal compound complex set forth in equation(2) has two Cl ligands connected to the Pd atom and also two functionalgroups. Further, it could have one Cl ligand and three functionalgroups, or, as in the complex of equation (1), three Cl ligands and onefunctional group. On the other hand, the insoluble metal compoundcomplexes may have a total of three, five, six, seven, or eight ligandsand functional groups. At least one functional group must be present.

The insoluble oxide-bound metal compound complex is furthercharacterized by its quantitive composition as set forth above.

The insoluble oxide-bound metal compound complexes are used herein ascatalysts in carrying out the present organic compound conversionreactions. Said reactions are those which are catalyzed by solublecompounds of the metals set forth hereinbefore in homogeneous catalysis.For example, one such conversion reaction is hydrogenation, involvingcompounds having carbon-to-carbon unsaturation, as in the conversion ofacetylenes, olefins, and diolefins, using complexes containing compoundsof platinum, palladium, ruthenium and/or rhodium. For carrying outcatalytic reactions generally, complexes containing as the central metalatom any of the metals described in the preceding paragraphs are of use.

Other catalytic reactions of the present invention include carbonmonoxide-insertion reactions, double bond isomerizations, vinyl esterinterchange reactions, and olefin (e.g. ethylene) oxidation reactions.Further examples of reactions of the present invention include olefinhydroformylation, comprising the reaction of an olefin with carbonmonoxide and hydrogen in the presence of complexes containing nickel,cobalt, or rhodium carbonyl moieties; olefin dimerization andpolymerization in the presence of nickel or rhodium chloride-containingcomplexes; olefin hydrocarboxylation, hydroesterification, andhydrocyanation in the presence of complexes containing a metal carbonylmoiety, or metal hydrocarbonyl moiety, or metal phosphine-substitutedcarbonyl moiety; conversion of CO and H₂, or alcohol and CO and H₂, tomixtures of hydrocarbons and/or alcohols; hydroquinone synthesis fromacetylenes, carbon monoxide, and water; or the cyclooligomerization ofacetylene to benzene and the like; the cyclooligomerization of butadieneto cyclooctadiene; or the carbonylation of acetylenes and olefins toacids. Also, acetylenes may be hydrated over rutheniumchloride-containing complexes. It will be apparent that many of thesereactions involve the conversion of unsaturated compounds, particularlyof unsaturated hydrocarbons like olefins and acetylenes. Referring againto ethylene oxidation, this reaction may be run in several ways; thus,ethylene may be oxidized in aqueous solution to produce acetaldehyde, orit may be oxidized in methanol solution to give vinyl methyl ether, orin acetic acid solution to produce vinyl acetate.

In view of the fact that the complex catalyst for use herein may containsome functional groups, i.e., basic groups, as well as metal compoundgroups, it follows that the complex may be a dual functional catalystcontaining two types of sites, basic sites and metal compound sites.Functionalized zeolites can contain acidic sites in addition to themetal compound sites. It is thus useful to catalyze polystep catalyticorganic reactions at low temperature and in the liquid phase. In such areaction, one type of catalytic site catalyzes a reaction step differentfrom that catalyzed by another type of site. The different types ofsites are separated by distances of the order of molecular dimensions.

In some reactions, both liquid and gaseous reactants take part and aresuitably catalyzed by the complexes. In all reactions, ease of catalystseparation by conventional operations of filtration, decantation, orcentrifugation is a characteristic, whether the products and/orreactants are liquid or gaseous. The reactions may be carried out inconventional fixed bed flow reactors, or in continuously stirred flowreactors, or in batch reactors.

In general, organic compounds may be catalytically converted in thepresence of the above heterogeneous catalyst materials over a wide rangeof catalytic conversion conditions, including a reaction temperature offrom about -80° C. to about 400° C., preferably from about -20° C. toabout 350° C., a reaction pressure of from about 0.1 atmosphere to about10,000 atmospheres, preferably from about atmospheric to about 1000atmospheres, and a contact time of between about 0.1 second and about 2hours, preferably between about 1 second and about 1 hour.

In particular, when the conversion of organic compound (e.g. hydrocarboncompound) by the present method is hydroformylation, catalyticconversion conditions should be maintained within certain criticalranges, including a temperature of from about 25° C. to about 300° C.,preferably from about 75° C. to about 200° C., a pressure of from aboutatmospheric to about 150 atmospheres, preferably from about 30atmospheres to about 100 atmospheres, a contact time of from about 5minutes to about 2 hours, preferably from about 12 minutes to about 1hour. During hydroformylation in the presence of the above heterogeneouscatalyst, a hydrogen/CO mole ratio should be maintained at between about0.3 and about 3, preferably between about 1 and about 2; and ahydrogen/organic compound (e.g. hydrocarbon compound) ratio should bemaintained at from about 0.5 to about 10 scf/bbl, preferably from about1 to about 5 scf/bbl.

Further, when the conversion of organic compound (e.g. hydrocarboncompound) by the present method is olefin dimerization, catalyticconversion conditions should be maintained within certain criticalranges, including a temperature of from about -80° C. to about 50° C.,preferably from about -20° C. to about 20° C., a pressure of from about0.1 atmosphere to about 100 atmospheres, preferably from aboutatmospheric to about 10 atmospheres and a contact time of from about 0.1second to about 10 seconds, preferably from about 1 second to about 5seconds. When the conversion is Fischer-Tropsch, catalytic conversionconditions should be maintained within different ranges, including atemperature of from about 100° C. to about 400° C., preferably fromabout 150° C. to about 350° C., a pressure of from about 0.1 atmosphereto about 10,000 atmospheres, preferably from about atmospheric to about1000 atmospheres, a contact time of from about 4 seconds to about 80seconds, preferably from about 20 seconds to about 60 seconds and ahydrogen/CO mole ratio of from about 0.2 to about 5, preferably fromabout 1 to about 3.

It is noted that a particular advantage of the oxide-bound metalcomplexes used in the present invention is their high thermal stabilitywhich allows their use in reactions at temperature in which liquid phaseis not easily obtained or at temperatures which would be high enough todegrade or collapse the pore structure of the polymer-bound metalcomplexes. Also, an advantage of the amine functional groups, incomparison with phosphine functional groups, is the high oxidativestability of the former.

In order to more fully illustrate the present invention, the followingspecific examples are presented. Said examples, it will be appreciated,are not meant to be, and should not be taken as, unduly limiting in anyway.

EXAMPLE 1

A 50 gram portion of small-pore silica was suspended in 250 ml. ofxylene containing 10 ml. ofN-(β-aminoethyl)-γ-aminopropyltrimethoxysilane. It was then heated toreflux (approx. 69° C.) for four hours and cooled to room temperature.The solvent was decanted and the product was washed three times with 250ml. portions of n-hexane. The product was then suspended in 125 ml. of88% formic acid and 100 ml. of 37% formaldehyde. The resultingsuspension was refluxed for six hours and cooled. The solvent wasdecanted and the product washed with water until neutral and then boiledin 300 ml. of water for one hour. The water was then decanted and theproduct washed two times with 300 ml. portions of acetone and dried in avacuum oven at 125° C. for two hours. Yield was 53.8 grams of substancehaving the structural formula: ##STR3##

Analysis of the above product showed 0.3% N.

Five grams of the above functionalized oxide product was suspended in150 ml. benzene through which CO had been bubbled for 15 minutes. A 0.15gram portion of [Rh(CO)₂ Cl]₂ was completely dissolved therein and themixture was warmed to 50°-55° C. for 16 hours and then cooled. The brownproduct was filtered out, washed and dried. Analysis of this productshowed 1.86% C, 1.63% H and 0.26% Rh.

EXAMPLE 2

A 15.0 gram portion of the functionalized oxide of Example 1 wassuspended in 200 ml. benzene through which CO had been bubbled for 15minutes. A 0.83 gram portion of [Rh(CO)₂ Cl]₂ was completely dissolvedin this system. The resulting mixture was then heated to 50°-55° C. for16 hours and cooled. The brown product was discernable from the clear,colorless supernatant solution and was filtered out, washed withbenzene, methanol and petroleum, ether, and dried under vacuum at 120°C. for 1/2 hour. Analysis of this product showed 1.86% C, 1.63% H and0.81% Rh.

EXAMPLE 3

A 50 gram portion of a commercial large-pore silica was suspended in 300ml. concentrated HCl; the mixture was heated to reflux (107° C.) for 4hours and then cooled. The silica was filtered out, washed withdistilled water until the wash water was neutral, washed with acetone,and dried in a vacuum oven at 125° C. for 16 hours. Yield was 47.75grams (loss was probably mechanical). This material was then suspendedin 300 ml. toluene; 27.5 grams dichlorodimethylsilane was dissolved in100 ml. toluene and added. The mixture was then heated to reflux (104°C.) for 4 hours and cooled. The mixture was reduced to a volume of 100ml. on a rotary evaporator at about 90° C. and about 20 mm. Hg pressure.A 10 gram portion of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane wasdissolved in 100 ml. toluene and added to the above mixture. Allvolatile liquids were then removed by distillation in a rotaryevaporator. Yield was 56.4 grams. An 18.3 gram portion of this materialwas placed in a glass tube and heated to 150° C. for 2 hours while airwas drawn through the tube at about 1 liter/minute. Yield was 17.7grams. This product was then suspended in 45 ml. of 91% formic acid and36 ml. of 37% formaldehyde solution. The mixture was stirred and heatedto reflux (89° C.) for 6 hours and then cooled. The product was filteredout and washed with distilled water until the wash was neutral. It wasthen stirred in water at 90° C. for 1 hour, filtered, washed withacetone and dried in a vacuum oven for 3 hours. Yield was 15.1 grams(most loss was probably mechanical). Analysis of this product showed3.54% C, 1.05% H, and 0.5% N.

The initial step of refluxing in HCl was to convert some surfacehydroxyl groups to surface chloride groups and thus activate the surfacefor condensation reactions. The condensation with dimethyldichlorosilanecreates a surface on which some pairs of surface hydroxyls or chloridesare converted to surface methyls as follows. ##STR4## This made thesurface less acidic and partially changed it from hydrophilic tohydrophobic. In addition, the following modifications resulted: ##STR5##This produced a site good for further condensation since it is flexibleand reduces steric requirements in the next step and also causes thefinal ligands to be farther away from the surface.

The procedure for putting on the amine ligand gave a product in which(1) the aminosilane was partially polymerized (at the silane end) as itwas deposited, and (2) this polymer was connected to the surface throughmore than one of the above flexible sites (and possibly to originalsurface sites as well). The result was a more firmly bonded ligandbecause a number of siloxane bonds would have to be broken for an aminefunction to be removed.

For the preparation of a catalyst, 5.0 grams of the above product wassuspended in 150 ml. benzene through which CO had been bubbled for 15minutes. A 0.16 gram portion of [Rh(CO)₂ Cl]₂ was completely dissolvedin this system; the mixture was warmed to 50°-55° C. for 6 hours andcooled. The product was brown and the supernatant solution clear andcolorless. The product was filtered out, washed with benzene, methanoland petroleum ether, and dried under vacuum at 120° C. for 1/2 hour.Yield was 4.9 grams (most loss probably mechanical). Analysis of thisproduct showed 0.81% Rh.

EXAMPLE 4

To 50 grams of silica suspended in 250 ml. xylene was added 10.4 gramsN-(β-aminoethyl)-γ-aminopropyltrimethoxysilane and 0.1 gramp-toluenesulfonic acid. The mixture was stirred under reflux for 4hours, cooled, washed with n-hexane, and dried in a vacuum oven at 120°C. for 16 hours. This material was then suspended in 100 ml. 88% formicacid and 75 ml. 37% formaldehyde and stirred under reflux for 16 hours.After cooling to room temperature, 100 ml. 0.1N HCl was added and themixture stirred for 10 minutes. The silica was filtered out, suspendedin water; 1N NaOH was added until the solution was neutral; and thesilica was then filtered out and washed with 1 liter of water. Thesilica was resuspended in 400 ml. water and the mixture was concentratedby evaporation at approximately 100° C. to about half of the originalvolume. (This step is designed to remove any silane not covalentlybonded to the silica). The silica was then filtered out and dried in avacuum oven at 120° C. overnight. The product contained 4.06% C and1.12% N.

Carbon monoxide was bubbled through 100 ml. benzene for 15 minutes, 1.29gram Rh₂ (CO)₄ Cl₂ was dissolved in the benzene by warming, and 9.0grams of the above functionalized silica was added. The mixture wasstirred at 60° C. for 16 hours, and the silica was filtered out, washedwith benzene and dried in a vacuum oven at 130° C. for 2 hours. Theproduct contained 6.84% rhodium.

EXAMPLE 5

This catalyst was prepared as in Example 4 through the step prior torhodium incorporation. It was further treated as described below toconvert any free surface silanol groups to trimethylsilyl groups beforethe rhodium was incorporated. Twenty-five grams of catalyst wassuspended in 250 ml. dried xylene and 10 ml. N,O-bis(trimethylsilyl)-acetamide was added with stirring. The mixture wasmaintained at 100° C. for 4.5 hours and then at 50-55% C for 16 hours.The silica was filtered out, washed with boiling water to removeacetamide, rinsed with acetone and dried in a vacuum oven. Rhodium wasthen added in the same way as in Example 3. The final product contained4.55% C, 0.87% N, and 1.96% Rh.

EXAMPLE 6

Thirty grams silica, 6.25 gramsN-(βaminoethyl)-γ-aminopropyltrimethoxysilane, and 120 ml. benzene werecharged to a 300 ml. autoclave and heated to 300° C. (approx. 900 psi)with stirring for 3 hours. After cooling, the product was washed asafter the condensation step in Example 4, and the synthesis wascontinued as in Example 4, except that a lower loading of rhodium wasadded. The final product contained 4.00% C, 0.55% N, and 1.26% Rh.

EXAMPLE 7

This catalyst was prepared from a portion of an intermediate materialmade in the preparation of the catalyst of Example 6, so the preparationwas the same up to the incorporation of the metal salt. An 8.0 gramportion of the silica that had been treated withN-(β-aminoethyl)-γ-aminopropyltriethoxysilane and then with a formicacid/formaldehyde solution followed by the usual work-up was thensuspended in 100 ml. of a 1/1 (vol./vol.) mixture of methanol/acetonethrough which carbon monoxide had been bubbled for 0.25 hour. Then 0.2gram Ru (CO)₂ Cl₂ was added and the mixture was warmed with stirring toreflux temperature (58° C.). Bubbling of CO through the system wascontinued, an additional 100 ml solvent was added, and reflux wascontinued for 16 hours. The silica was filtered out, washed thoroughlywith methanol, and dried in vacuo at 125° C. for 0.5 hour. The catalystcontained 4.5% carbon, 0.94% hydrogen and 0.6% nitrogen.

EXAMPLE 8

This catalyst was prepared from a portion of an intermediate materialmade in the synthesis of the catalyst of Example 5. A 12.0 gram portionof material was removed from the preparation of the catalyst of Example5 just prior to the treatment with N,O-bis (trimethylsilyl)-acetamide.Instead, it was suspended in 300 ml. benzene through which carbonmonoxide had been bubbling for 0.25 hour and 0.15 gramdicobaltooctacarbonyl was added. Bubbling of CO was continued and themixture was heated to 62° C. for 0.5 hour, cooled, washed thoroughlywith hexane and petroleum ether and dried. The product contained 4.50%carbon, 1.23% hydrogen, 1.1% nitrogen, and 0.42% cobalt.

EXAMPLE 9

gamma-Alumina was made by heating α-alumina for 3 hours at 900° F. inair. This material was treated withN-(β-aminoethyl)-γ-aminopropyl-trimethoxysilane by the procedure ofExample 4 and then treated with formic acid/formaldehyde and worked up,also by the procedures of Example 4. It was then treated withN,O-bis(trimethylsilyl)-acetamide by the procedure of Example 5 and thenwith Rh₂ (CO)₄ Cl₂ by the procedure of Example 4. The final productcontained 15.0% carbon, 2.2% hydrogen, 0.32% nitrogen and 0.33% rhodium.

EXAMPLE 10

A 10 gram sample of synthetic zeolite Y is suspended in water for 4hours and removed by filtration but allowed to stay wet and thensuspended in 4 ml N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, 0.03grams p-toluenesulfonic acid, and 60 ml xylene. The mixture is stirredunder reflux for 16 hours. The sample is filtered out, washed withn-hexane, and dried in a vacuum oven. It is then suspended in 200 ml.benzene through which CO has been bubbled for 15 minutes. A 0.8 gramportion of [RH(CO)₂ Cl]₂ is added to the suspension. The resultingsystem is heated to 50°-55° C. for 16 hours with continuing CO flow. Theproduct is filtered out, washed with benzene, methanol, and petroleumether and dried under vacuum at 120° C. for 4 hours.

EXAMPLE 11

To demonstrate that the amine functional member of the catalyst for useherein may be a substituted amine, e.g. a phosphinoamine, a substitutedaminosilane functionalized silica was prepared as follows:

Three hundred grams of silica gel was suspended in xylene and heated tothe reflux temperature. To this was added 45 grams of chloromethylmethyl silane and the mixture was stirred and heated at refluxovernight. The mixture was cooled to about 50° C.; 10.0 ml oftrimethylchlorosilane was added and the mixture was allowed to cool andstand overnight. The product was isolated by filtration and washed withxylene, hexane, and petroleum ether and was found by analysis to contain2.73% Cl, 2.07% C, and 0.71% H on a weight basis.

Sixty ml. (24.7 grams) of the above product was further modified bysuspending it in 60 ml. of dimethylformamide and 22.5 grams ofethylamine and heating to 150° C. for 10 hours. The reaction mixture wascooled and the product isolated by filtration. It was then washedsequentially with hexane, water, dilute NH₄ OH, water 1% HCl, water,dilute NH₄ OH, 2% NaOH, water (until neutral), methanol, and petroleumether. Analysis of the final product showed it to contain on a weightbasis 0.18% N, 1.0% C, and 0.61% H.

Ten grams of the above amine functionalized silica was further modifiedby suspending it in 50 ml. of chloroform containing 10 ml. ofethylamine. To this stirred mixture was slowly added 5.0 ml. ofbis-isopropylchlorophosphine. The reaction mixture was allowed to standovernight, the product was isolated by filtration, and washedsequentially with chloroform and petroleum ether, and dried under N₂.The final product was analyzed and found to contain on a weight basis5.1% C, 1.5% H, 0.6% Cl, 0.13% N, and 1.1% P. This product containedamine functional members which may be referred to as aminophosphinefunctional members wherein attached to many nitrogen atoms whichpreviously had hydrogen atoms associated therewith were phosphinemembers as substitutions for the hydrogen atoms.

EXAMPLE 12

The functionalized silica of Example 11 was used to make a catalyst forthe dimerization of propylene. Fourteen ml. (5.4 grams) of thefunctionalized silica was suspended in 100 ml. of chlorobenzene and 100ml of a 0.0026 M solution of Ni(acac)₂ in chlorobenzene was added. Thesolution was refluxed with gentle stirring for two hours and cooled. Thesupernatent liquid was decanted in a drybox and the solid, after washingwith 100 ml. chlorobenzene, was vacuum dried. Analysis on a weight basiswas 0.84% P, and 0.24% Ni.

The catalysts for use herein are useful in organic compound conversion,such as, for example, hydroformylation, oxidation, oligomerization,dimerization, hydrogenation, Fischer-Tropsch hydrocarbon synthesis andothers. They exhibit excellent thermal stability up to a temperature ofabout 400° C., while the heterogeneous resin catalysts are stable onlyup to about 200° C.

For the purpose of illustrating the organic compound conversion of thepresent invention, the following test procedure was adapted:

Each test was conducted in a stirred 300 ml. autoclave whereby liquidsand gases could be added and removed while the autoclave reaction systemwas under pressure. In each test, 1 to 2 grams of catalyst and 90 ml.solvent, e.g., benzene or 1:8 (volume/volume) methanol-benzene, werecharged to the reactor, which was then pressure-tested with CO andvented. The system was heated to reaction temperature and thenpressurized with 1:1 hydrogen:carbon monoxide. Then 20 ml. 1:1l-hexene:n-octanal was added and the reaction started. Pressure wascontrolled at 1000 psi, or gas was added periodically so that thepressure fluctuated between about 900 and 1000 psi. Samples werewithdrawn and the total product analyzed by gas chromatography on aCarbowax 1000 column, and C₆ hydrocarbons on a TCP column. Liquidsamples were analyzed for Rh and N. Used catalysts were analyzed for Rh,C and N.

Since the formation of aldehydes and alcohols from olefins can be shownto conform to the following scheme, the absolute values of all the rateconstants of the reactions were determined. ##STR6## The n-octanal wasincluded in the reaction mixture for ease of kinetic evaluation of thecatalysts.

Assuming that aldehyde diacetals were in rapid equilibrium with thecorresponding aldehydes, the hydrogenation rate was measured by thedisappearance of the total thereof. S_(L) =100 k₁ /(k₁ +k₂) was ameasure of the linearity of the hydroformylation products from 1-olefin.S_(I) =100 k_(F) /(k₁ +k₂ +k_(F)) was a comparison of the rates ofisomerization and hydroformylation of 1-olefins. These two functions areimportant because in most applications normal aldehydes are preferred.S_(AC) was defined as the percent diacetal in the linear product at thespecified time. S_(AL) was defined as the ratio of the rate of"steady-state" alcohol formation to the rate of "steady-state" totalolefin conversion. The specific rate constants k₁ and k₂, corrected forRh loading, reaction volume, etc., gave a measure of the relativeactivities of the catalysts tested.

Results of the organic compound conversion test hereinabove defined onthe catalyst samples prepared by examples herein are tabulated in TableI. For comparison, an amine functionalized polymer ##STR7## was used asa catalyst as well. The table clearly shows somewhat lower activity forthe polymer catalyst and its lack of activity for the formation ofacetate.

                                      TABLE I                                     __________________________________________________________________________    Organic Compound Conversion.sup.(1) of Catalyst Species                       Catalyst of                                                                   Example                                                                             S.sub.L                                                                          S.sub.I                                                                          S.sub.AC.sup.(4)                                                                   S.sub.AL × 10.sup.3                                                            (k.sub.1 + k.sub.2) × 10.sup.3                                                  Time.sup.(5)                                                                      Conversions.sup.(6)                       __________________________________________________________________________    3     75.6                                                                             55.8                                                                             1      0    357     2.5 99                                          3.sup.(2)                                                                         71.8                                                                             60.8                                                                             2.7    0    530     4.3 100                                       4     79.6                                                                             60.7                                                                             19   1.3    136     7.4 100                                         4.sup.(3)                                                                         71.5                                                                             82.8                                                                             --   2.8    .52     21  98                                        5     71.2                                                                             63.5                                                                             31   approx. 1                                                                            910     2.5 99                                        6     74.8                                                                             46.8                                                                             0.2  9.4    396     2.0 99                                        9     73.1                                                                             56.3                                                                             0    --     1,237   2.0 99                                        (Polymer)                                                                           74 67 0    0      154     6.0 84                                        __________________________________________________________________________     .sup.(1) Hydroformylation of 1hexene at 100° C. 1000 psi and with      methanol/benzene solvent.                                                     .sup.(2) Catalyst from above run reused after cleaning by 1 hour reflux i     MeOH/benzene                                                                  .sup.(3) Hydroformylation of 1hexene at 100° C. 1000 psi and with      benzene solvent.                                                              .sup.(4) At time indicated.                                                   .sup.(5) Time of run in hours                                                 .sup.(6) Total olefin conversion.                                        

EXAMPLE 13

Propylene was dimerized in a vertical downflow reactor over 2 cc of thecatalyst of Example 12 diluted with 2 cc of 50/80 mesh Vycor chips. Thecatalyst was first pretreated with a solution of 0.2 M (diethylamino)di-isopropyl phosphine at 0° C. A 58% propylene/42% propane mixture wasfed at a rate of 50 ml/minute over the catalyst together with a solutionof 0.052 M aluminum sesiquichloride in chlorobenzene at a rate of 7.3ml/hour. This corresponds to 3 WHSV based on total catalyst and 1250WHSV based on nickel. The conversion remained essentially constant atabout 50% for 6.5 hours and the selectivity of dimethyl butenes variedbetween 23 and 70%. Typical product compositions were 88 % dimers, 8%trimers, and 4% higher oligomers.

To further illustrate an organic compound conversion process utilizingthe catalyst of the present invention, a Fischer-Tropsch reaction systemwas employed with catalysis therein by the catalyst hereof. Reactionconditions and results thereof are listed in Table II. Under thesetemperature conditions, a polymer bound metal complex would not beusable because of the thermal instability of the polymer.

                  TABLE II                                                        ______________________________________                                                                   Tem-                                               Catalyst         Pressure, pera-                                              of               psig.     ture,                                              Example                                                                              Reactants H.sub.2                                                                              CO   °C.                                                                          Time.sup.(1)                                                                        Yield.sup.(2)                        ______________________________________                                        7      1-butanol.sup.(3)                                                                       500    500  300   12.5  6.8                                  7      n-propanol                                                                              500    500  300   96    approx. 6                            7      1-hexene/ 500    500  300   96    approx. 5.sup.(4)                           n-propanol                                                             8      1-octanol/                                                                              500    500  300   26    approx. 5.sup.(6)                           1-hexene.sup.(5)                                                       ______________________________________                                         .sup.(1) Reaction time in hours.                                              .sup.(2) Percent yield of products having a higher boiling point than the     reactants (not including hydroformylation products).                          .sup.(3) Benzene solvent.                                                     .sup.(4) Hydroformylation products also noted.                                .sup.(5) Methanol and 1,2,4trimethylbenzene solvents.                         .sup.(6) Hydroformylation and olefin isomerization products also noted.  

What is claimed is:
 1. In the method for hydroformylation of an olefinto produce aldehydes and alcohols, said process comprising reacting amixture of said olefin with carbon monoxide and hydrogen underconversion conditions including a temperature of between about 25° C.and about 300° C., a pressure of between about atmospheric and about 150atmospheres, a contact time of between about 5 minutes and about 2hours, a hydrogen/carbon monoxide ratio of between about 0.3 and about3, and a hydrogen/olefin ratio between about 0.5 scf/bbl and about 10scf/bbl, said reacting being conducted by contacting said mixture with ahydroformylation catalyst, the improvement which comprises utilizing assaid hydroformylation catalyst a catalytic material which comprises asubstrate of a porous refractory oxide, said substrate having surfacehydroxyl groups, a minimum surface area of about 10 m² /g and pores witha minimum pore diameter of about 5 Angstrom Units, and substrate beingmodified by at least one amine functional member, containing the elementsilicon, coordinated to a metal function of a transition metal selectedfrom the group consisting of nickel, cobalt and rhodium, said aminefunctional member acting as a bridging member between said substrate andsaid metal function, as a ligand covalently bonded to said substrate. 2.The method of claim 1 wherein the substrate of said catalyst has aminimum surface area of about 200 m² /g and has a minimum pore diameterof 100 Angstrom Units.
 3. The method of claim 1 wherein the substrate ofsaid catalyst has a major component of silica or alumina.
 4. The methodof claim 1 wherein the substrate of said catalyst is selected from thegroup consisting of alumina, silica, silica combined with an oxide of ametal of Groups IIA, IIIA, IVA, IIIB, IVB or VB or the Periodic Table ofElements, open lattice clays and crystalline aluminosilicates.
 5. Themethod of claim 4 wherein the substrate of said catalyst is silica orsilica combined with an oxide of a metal or Groups IIA, IIIA, IVA, IIIB,IVB or VB of the Periodic Table of Elements.
 6. The method of claim 4wherein the substrate of said catalyst is a crystalline aluminosilicate.7. The method of claim 6 wherein said crystalline aluminosilicate is asynthetic zeolite.
 8. The method of claim 6 wherein said crystallinealuminosilicate is a natural zeolite.
 9. The method of claim 4 whereinthe substrate of said catalyst is alumina.
 10. The method of claim 4wherein the substrate of said catalyst is silica and the metal functionof said catalyst is rhodium or ruthenium.
 11. The method of claim 1wherein the amine functional member of said catalyst is made from acompound selected from the group consisting ofN-(β-aminoethyl)-γ-aminopropyltrimethoxysilane andN-(β-aminoethyl)-γ-aminopropyltriethoxysilane.
 12. The method of claim 1wherein said amine functional member is a phosphinoamine.
 13. The methodof claim 2 wherein said amine functional member is a phosphinoamine. 14.The method of claim 3 wherein said amine functional member is aphosphinoamine.
 15. The method of claim 4 wherein said amine functionalmember is a phosphinoamine.
 16. The method of claim 1 wherein theconversion conditions include a temperature of between about 75° C. andabout 200° C., a pressure of between about 30 atmospheres and about 100atmospheres, a contact time of between about 12 minutes and about 1hour, a hydrogen/carbon monoxide ratio of between about 1 and about 2and a hydrogen/olefin ratio between about 1 scf/bbl and about 5 scf/bbl.17. The method of claim 1 wherein the olefin is 1-hexene, the aldehydesproduced are heptanals and the alcohols produced are heptanols.